Substituted O-{8 aminosulfonyl{9 -glycolic amides

ABSTRACT

New and valuable substituted O-(aminosulfonyl)-glycolic amides and their use as herbicides.

United States Patent 1 1 Fischer et al.

[73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschafl, Ludwigshafen Rhine, Germany [22] Filed: Apr. 16, 1973 [21] Appl. No.: 35l,240

[30] Foreign Application Priority Data Apr. 22, 1972 Germany P 22 19 923.l

[52] US. Cl 260/239 B; 71/88; 71/89; 71/91; 7l/94; 71/95; 260/239 BA; 260/243 B; 260/247.l R; 260/247.7 V; 260/268 C; 260/293.85; 260/293.86; 260/3265 S;

[ 51 May 13, 1975 [5 [1 Int. CL. C07d 41/04; C07d 27/04; C07d 29/34 [58] Field of Search 260/239 B, 456 A, 293.85, 260/3265 S, 239 BA [56] References Cited UNITED STATES PATENTS 3,536,721 ll/l970 Soong et al. 260/239 3,798,254 3/l974 Phillips .i 260/293.85

Primary ExaminerAlton D. Rollins Assistant Examiner-Mark L. Berch Attorney, Agent, or FirmJohnston. Keil, Thompson & Shurtleff [57] ABSTRACT New and valuable substituted O-[aminosulfonyl]- glycolic amides and their use as herbicides.

9 Claims, N0 Drawings 1 SUBSTITUTED O-l AMINOSULFONYL1-GLYCOLIC AMIDES This present invention relates to new and valuable substituted O-laminosulfonyll-glycolic amides; their use as herbicides; and herbicides containing these com pounds as active ingredients.

It is known to use chloroacetic acid-N-isopropyl anilide as a herbicide. However, its action is only poor.

We have now found that substituted [aminosulfonyll-glycolic amides of the formula l it-c-cH H 2 0 NHR, O 0

where R denotes hydrogen, alkyl (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, hexyl), cycloalkyl (cyclopentyl, cyclohexyl) or haloalkyl (a-chloroethyl) and the carbonamide nitrogen is a ring member of an unsubstituted or lower-alkylsubstituted monocyclic or bicyclic cycloalkylimine which may contain further hetero atoms in the ring, have a better herbicidal action.

The following imines may be part of the carbonamide function: Polymethylenimines:

e.g., tetramethylenimine, Z-methylpentamethylenimine, 3-methylpentamethylenimine, 4-methylpentamethylenimine, 2,4- dimethylpentamethylenimine, 2,5-dimethylpentamethylenimine, 2,6-dimethylpentamethylenimine, 2,4,6- trimethylpentamethylenimine, hexamethylenimine, Z-methylhexamethylenimine, 3-methylhexamethylenimine, 4-methylhexamethylenimine. heptamethylenimine. octamethylenimine, 3-azabicyclo-[3,2,2]-

nonane.

Morpholines:

e.g., morpholine, 2-methylmorpholine, 2.5-dimethylmorpholine, 2,6-dimethylmorpholine, thiomorpholine, thiomorpholine-S,S-dioxide.

Piperazine:

e.g., l-methylpiperazinev The new compounds may be used as herbicides in amounts of from 0.1 to kg/hectare before sowing. after sowing but preemergence, and after emergence of the crop plants.

They are particularly effective on grasses (Gramineae) and are suitable for use as herbicides in for instance the following crops: Indian corn (Zea mays). soybeans [Glycine max.(hispida)], cotton (Gossypium hirsurum), beet (Beta vulgaris), sorghum (Sorghum bicolor), rape (Brassica napus), peas (Pisum sativum), beans (Phaseolus vulgaris) and lettuce (Lacmca saliva).

The new compounds may be prepared by reacting a substituted glycolic amide with an aminosulfonyl chloride in the presence of an acid acceptor, e.g., triethylamine and pyridine.

pentamethylenimine,

EXAMPLE 1 0-[isopropylaminosulfonyl]-glycolic hexamethyleneamide At 0C, a solution of 32 parts by weight of isopropylaminosulfonyl chloride in 92 parts by weight of dichloromethane was added to a solution of 23.6 parts by weight of glycolic hexamethyleneamide and 20.2

parts by weight of triethylamine in 660 parts by weight of dichloromethane.

After 2 hours the mixture was washed with dilute hydrochloric acid, then with water, with sodium bicarbonate solution and again with water. The organic phase was dried with magnesium sulfate and concentrated in vacuo. The crude product obtained melts at C to 82C; the pure compound may be obtained by recrystallization from a mixture of benzene and ligroin and melts at 87 to 88C.

The compound has the following structural formula;

The compounds listed below may be obtained analogously:

[05 to 107 [(17 to W9 [(10 to l()l 59 to (1| 44 to 46 hcxamcthyleniminc H pentamcthyleniminc 124 to I26 I25 to 127 B3 to R5 98 to NH 2-mcthylpcntamcthylcniminc CH a rI s ia cyclopentyl cyclohcxyl 2-chloroethyl H 3-methylpcntamcthylenimine CH fi UI cyclopentyl cyclohexyl Z-chlorocthyl H -Continued 3-mcthylpcntamcthylcnimine -mcthylpcntamcthylcniminc 2.6-dimethylpentamethyleniminc 3-azabicyclo-l 32.2 I -nonane morpholine 1.

2,6-dimethylmorpholine 13910141 11110113 116 to 117 78to 80 105 to 107 911093 92t094 88 I099 -Continued C l-l 2.6-dimethyl morpholine 8 I3 cyclopentyl cyclohexyl 2-chloroethyl H thiomorpholine-S.S-dioxide CH3 3-ethyl-4-methylpentamethylenimine 70 to 71 43 to 44 The substituted glycolic amides used as starting materials may be prepared by known methods, e.g., glycolic heptamethyleneamide is obtained by reacting heptamethylenimine with l,3-dioxolane-2,4-dione (cf. Chem. Soc., 1357, (1951)).

EXAMPLE 2 N-C-CH OH H 2 Glycolic amides are also obtained by subjecting the amine glycolates to thermal elimination of water.

EXAMPLE 3 Glycolic hexamethyleneamide A mixture of 480 parts by weight of hexamethylenimine and 670 parts by weight of 57% aqueous glycolic acid was heated at 195 to 210C until no more water distilled off. Subsequently the residue was distilled in vacuo.

Boiling point (0.1 mm Hg): 115 to 125C; n 1.4990.

The compound has the following structural formula:

N-C-CH OH K./ II 2 The following glycolic amides may be prepared as in Examples 2 and 3:

mp. 42 to 44C m. 59 to 41C 2 6 rug-011 011 rb-c-ca on mp. 54 to 56% mp. 70 to 72C mp. 164 to 166C b.p. 10a to 115C used; in any case it should ensure a fine distribution of 5 the active ingredient.

For the preparation of solutions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils and oils of vegetable or mineral origin, and cyclic hydrocarbons such as tetrahydronaphthalene and alkylated naphthalenes are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by add ing water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e.g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be pre pared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent. Oils of various types may be added to ready-to-use spray liquors.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g., clay or fertilizers.

Granules may be prepared by bonding the active ingredients to solid carriers.

Directly sprayable dispersions may also be prepared with oils.

The new compounds may be mixed with fertilizers, insecticides, fungicides and other herbicides.

EXAMPLE 4 In the greenhouse loamy sandy soil was filled into pots and sown with the seeds of cotton (Gossypium hirsurum), soybeans (Soja hz'spida), beet (Bela vulgaris), slender foxtail (Alopecurus myosuroides), wild oats (Arena fame), annual bluegrass (Poa annua), goose grass (Eleusine indica), giant foxtail (Setaria faberii) and barnyard grass (Echinochloa crus-galli). The soil prepared in this manner was then treated with 1.5 kg/hectare of O-[isopropylaminosulfonyl]-glycolic hexamethyleneamide (I) and, for comparison, with 1.5 kg/hectare of chloroacetic N-isopropylanilide (1]), each compound being dispersed in 500 liters of water/- hectare.

After 4 to 5 weeks it was ascertained that active ingredient I had a better herbicidal action than ll, combined with the same good crop plant compatibility.

The results are given below:

Active ingredient no damage I00 complete destruction EXAMPLE 5 The plants cotton (Gossypz'um him-mum), soybeans (Soja lzispida), rice (Oryza saliva), lndian corn (Zea mays), beet (Beta vulgaris), slender foxtail (Alopec'urus myosuroides), bluegrass (Puu trivia/is), wild oats (Avenafatua), goosegrass (Eleusine indica yellow nutsedge (Cyperus esculenmx) and barnyard grass (Echinochloa crus-galli) were treated at a growth height of 3 to 17 cm with l kg/hectare of O-[isopropylaminosulfonyll-glycolic hexamethyleneamide (l) and, for comparison, with l kg/hectare of chloroacetic N- isopropylanilide (ll), each compound being dispersed in 500 liters of water/hectare.

After 3 to 4 weeks it was ascertained that active ingredient I had a better herbicidal action on the unwanted plants than ll, combined with superior compatibility with cotton, soybeans and beet.

The results are given below:

Active ingredient 90 parts by weight of compound I is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 7 20 parts by weight of compound I is dissolved in a mixture consisting of parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to l mole of oleic acid-N- monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8 20 parts by weight of compound I is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to l mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to l mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an

aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 9 EXAMPLE 10 20 parts by weight of compound I is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of III VII

VIII

water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 1 l 3 parts by weight of compound I is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 12 30 parts by weight of compound I is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE l3 In the greenhouse loamy sandy soil was filled into pots and sown with the seeds of various plants. The soil was then immediately treated with 1.5 kg/hectare of each of the following active ingredients each being emulsified or dispersed in 500 liters of water/hectare:

and for comparison,

After 4 to 5 weeks it was ascertained that active in- EXAMPLE l4 gredients I to IX had a better herbicidal action than X,

, ln the greenhouse various plants were treated at a combined with the same good Crop plant compatibility.

growth height of 3 to l7 cm with l kg/hectare of each of the following active ingredients, each compound being emulsified or dispersed in 500 liters of water/hec- The results are given below: tare:

Active ingredient I ll lll IV V VI VII Vlll IX X kgfhu Crop plants: Guxsvpium Iu'rsunmi U U O (J O U 0 U U Suju lnspida U U 0 O O O 0 U U 0 Bum \ulgurLt U 0 (J U U 0 O U U U Unwanted plants: Alupet'urus mym uruidm l U0 U0 l 00 l [)0 l 00 l 00 l 00 80 8 4O Arenufumu 95 9U 9U 75 75 5O 5O 85 95 3O Pun unmm lUU I00 I00 IOU 100 I00 95 9O 8U 6U Eleuxine indit'u 100 100 IOU 9O 9U 9U 95 8O 8O Seraria fuherii I00 100 IUD 100 lOO 95 7O 65 Et'liinucli/ou (TH.\' gulh' 100 100 I00 100 100 100 75 75 70 U no damage 101) complete destruction l IV 3-CH -O- -NH-CH v 8 CH C-CH -O--NH-CH u 2 O 0 CH i VI H -C-CH -O-SNH-CH n 2 u 5 O O (T 8 5 VII H N- C l-CH O-lS NH-CH \J O O CH 5 i? VIII I l? IX @EECH O'SENHC H H O O and, for comparison,

3H(cH X N-C-CH Cl 13 14 After 3 to 4 days it was ascertained that active ingremember of an unsubstituted or lower-alkyl-substituted dients l to 1X had a crop plant compatibility superior tetramethylenirnine, pentamethylenimine. hexameto that of X. thylenimine. heptamethylenimine, octamethylenimine.

The results are given below: or 3-azabicyclo-[3.2.2i-n0nane ring.

Active ingredient I ll III IV V VI VII VIII IX X kl/ha Crog lunts: Gussyplum hlrsumm 0 U 0 (J 0 0 0 t) it] Suja Irlspidu 0 O 5 5 l0 0 0 0 l0 Oryza saliva l5 l0 l5 l5 l5 0 0 0 U Zea mays 0 0 0 0 0 0 (J 0 l) 0 Beta vulgar-is 0 0 0 0 0 0 0 0 ll 5 Unwanted lantl: Alupet'urus myusuruides I00 90 80 [00 100 50 50 I00 75 40 Pm: lrfi'lulis 0s 90 so as 95 so so mu so so Arena falua 80 60 65 7O 70 40 8O 70 2t) Eleusine India: 95 90 90 95 95 30 30 70 60 i5 Cyperus rule-mus 75 75 70 70 7U 5U 50 6t) 50 45 Echimu'lrlua crusgal/l 100 r00 95 95 95 50 45 95 so 40 O I no damage IOU-complete Ll We claim: 25 2. O-[aminosulfonyll-glycolic hexamethyleneamide. l. A substituted O-[aminosulfonyll-glycolic amide of 3. O-[methylaminosulfonyl]-glycolic hexamethe formula thyleneamide.

4. 0-[ethylaminosulfonyl]-glycolic hexamethyleneamide.

5. O-[propylaminosulfonyl]-glycolic hexamethyleneamide. I N-c-CH -0-s-NHR, 6. O-[rsopropylammosulfonyl]-glycolrc hexamethyleneamide.

r O 7. O-[n-butylaminosulfonyl]-glycolic hexamethyleneamide.

8. O-[isobutylaminosulfonyll-glycolic hexamethyleneamide. where R denotes hydrogen, alkyl of one to six carbon 9. O [sec-butylaminosulfonyll-glycolic hexameatoms, cyclopentyl, cyclohexyl or haloalkyl of one to thyleneamide. six carbon atoms and the carbonamide nitrogen is a 

1. A SUBSTITUTED O-(AMINOSULFONYL)-GLYCOLIC AMIDE OF THE FORMULA
 2. O-(aminosulfonyl)-glycolic hexamethyleneamide.
 3. O-(methylaminosulfonyl)-glycolic hexamethyleneamide.
 4. O-(ethylaminosulfonyl)-glycolic hexamethyleneamide.
 5. O-(propylaminosulfonyl)-glycolic hexamethyleneamide.
 6. O-(isopropylaminosulfonyl)-glycolic hexamethyleneamide.
 7. O-(n-butylaminosulfonyl)-glycolic hexamethyleneamide.
 8. O-(isobutylaminosulfonyl)-glycolic hexamethyleneamide.
 9. O-(sec-butylaminosulfonyl)-glycolic hexamethyleneamide. 